[논문]저농도 황산 용액 및 2-스텝 침출 방법을 이용한 폐LiFePO4 양극재로부터 효율적인 리튬의 선택적 회수

김대원; 김희선

doi:10.7464/ksct.2023.29.2.87

저농도 황산 용액 및 2-스텝 침출 방법을 이용한 폐LiFePO4 양극재로부터 효율적인 리튬의 선택적 회수
Efficient Selective Recovery of Lithium from Waste LiFePO4 Cathode Materials using Low Concentration Sulfuric Solution and 2-step Leaching Method 원문보기

청정기술 = Clean technology, v.29 no.2, 2023년, pp.87 - 94

김대원 (고등기술연구원 신소재공정센터) , 김희선 (고등기술연구원 신소재공정센터)

초록
AI-Helper

폐리튬계 이차전지로부터 유가금속을 회수하는 것은 한정된 지구자원의 활용 측면에서 매우 중요하다. 최근 자동차의 전지로 많이 사용하고 있는 LiFePO₄ 전지 양극재 성분에는 리튬이 약 5.2% 함유되어 있으며, 사용 후 전지에서 리튬 재활용을 통하여 다시 전지의 원료로써 사용할 수 있다. 본 연구에서는 폐LiFePO₄ 양극재 분말에 함유된 리튬을 선택적으로 침출하기 위하여 일반적으로 많이 사용하고 있는 무기산의 일종인 저농도 황산을 이용하였다. 그리고 각 성분의 침출율 및 분리효율을 비교·분석을 위하여 침출 시 광액농도를 변수로 2 스텝 침출 공정을 적용하여 최적의 침출조건을 도출하고자 하였다. 광액농도를 변수로 침출 시 철 및 인 성분이 거의 침출되지 않는 200 g/L의 광액농도 조건에서는 타 조건과 분리 효율이 약 200배 이상 높은 것으로 확인되었다. 이에 리튬의 선택적 침출 및 회수에 있어서 침출조건을 최적화하였다.

Abstract ▼ AI-Helper

The recovery of valuable metals from waste lithium-based secondary batteries is very important in terms of efficiently utilizing earth's limited number of resources. Currently, the cathode material of a LiFePO4 battery, a type of battery which is widely used in automobiles, contains approximately 5% lithium. After use, the lithium in these batteries can be used again as a raw material for new batteries through lithium recycling. In this study, low-concentration sulfuric acid, a commonly used type of inorganic acid, was used to selectively leach the lithium contained in a waste LiFePO4 cathode material powder. In addition, in order to compare and analyze the leaching efficiency and separation efficiency of each component, the optimalleaching conditions were derived by applying a two-step leaching process with pulp density being used as a variable during leaching. When leaching with pulp density as a variable, it was confirmed that at a pulp density of 200 g/L, the separation efficiency was approximately 200 times higher than at other pulp densities because the iron and phosphorus components were hardly leached at this pulp density. Accordingly, the pulp density of 200 g/L was used tooptimize the leaching conditions for the selective leaching and recovery of lithium.

주제어

표/그림 (9)

표 Table1. Hydrometallurgical methods using the mineral acids for the recycling of waste LiFePO₄ batteries
$Figure 1. (a) X-ray diffraction pattern and (b)-(c) SEM image of waste LiFePO<sub>4</sub> powder.$ 그림 Figure 1. (a) X-ray diffraction pattern and (b)-(c) SEM image of waste LiFePO₄ powder.
표 Table 2. Chemical composition of waste LiFePO₄ cathode powders used this study and previous studies (%)
그림 Figure 2. Experimental procedure for the lithium separation/recovery of waste LiFePO₄ powder.
$Figure 3. X-ray diffraction pattern of leaching residue according to the pulp density from LiFePO<sub>4</sub> cathode powder (pulp density = 50 g/L, 100 g/L, 200 g/L).$ 그림 Figure 3. X-ray diffraction pattern of leaching residue according to the pulp density from LiFePO₄ cathode powder (pulp density = 50 g/L, 100 g/L, 200 g/L).
표 Table 3. Chemical composition and leaching rate of reaction leachate according to the pulp density from waste LiFePO₄ cathode powder
그림 Figure 4. The correlation of leaching rate according to the pulp density; (a) Li leaching rate, (b) Fe leaching rate, (c) P leaching rate.
그림 Figure 5. The correlation of leaching rate and separation rate % according to the pulp density at 1st and 1st+2nd leaching step ; (a) 1st, (b) 1st+2nd leaching step.
표 Table 4. Partition coefficient and separation efficiency of reaction leachate according to the pulp density from waste LiFePO₄ cathode powder

참고문헌 (43)

Ramana, C. V., Mauger, A., Gendron, F., Julien, C. M., and Zaghib, K., "Study of the Li-insertion/extraction process in LiFePO 4 /FePO 4 ," J. Power Sour., 187, 555-564 (2009).？
Kim, D. K., Park, H. M., Jeong, Y. U., Lee, J. H., and Kim, J. J., "The Effect of Synthesis on the Electrochemical Properties of LiFePO 4 for Cathode Material of Secondary Lithium Ion Batteries," J. Korean Ceramic Soc., 43(2), 121-125 (2006).？
Kong, M., Kim, H. S., and Gu, H. B., "Electrochemical Properties of LiFePO 4 Cathode Materials for Lithium Polymer Batteries," J. KIEEME, 19(6), 519-523 (2006).？
Hwang, Y. G., Kil, S. C., and Kim, J. H., "Technology Trends of Cathode Active Materials for Lithium Ion Battery," Resour. Recycl., 21(5), 79-87 (2012).？
Park, J. S., "The waste battery Industry," Report of Eugene Investment & Securities, (2022).？
Natarajan, S. and Aravindan, V., "Recycling strategies for spent Li-ion battery mixed cathodes," ACS Energy Lett., 3(9), 2101-2103 (2018).？
Chen, W. S. and Ho, H. J.,"Recovery of Valuable Metals from Lithium-Ion Batteries NMC Cathode Waste Materials by Hydrometallurgical Methods," Metals, 8(5), 321-227 (2018).？

상세보기
Joo, S., Kim, D. G., Byun, S. Y., Kim, Y. H., and Shim, H. W., "A Study on the Synthesis Behavior of Lithium Hydroxide by Type of Precipitant for Lithium Sulfate Recovered from Waste LIB," Resour. Recycl., 30(1), 44-52 (2021).？
Kim, D. W., Park, J. R., Ahn, N. K., Choi G. M., Jin Y. H., and Yang J. K., "A review on the recovery of the lithium carbonate powders from lithium containing substances," J. Korean Cryst. Growth Cryst. Technol., 29(3), 91-106 (2019).？
Jin, Y. H., Kim, B. R., and Kim, D. W., "Correlation between Lithium Concentration and Ecotoxicoloigy in Lithium Contained Waste Water," Clean Technol., 27(1), 33-38 (2021).？
Kim, B. R., Kim, D. W., Kim, T. H., Lee J. W., Jung, H. C., Han, D. H., Jung, S. H., and Yang, D. H., "A study on the Synthesis of Cathode Active Material Precursor from Waste Lithium Secondary Battery," J. Korean Cryst. Growth Cryst. Technol., 32(2), 61-67 (2022).？
Jung, Y. J., Park, S. C., Kim, Y. H., Yoo, B. Y., Lee, M. S., and Son, S. H., "A Study on Optimization of Nitric Acid Leaching and Roasting Process for Selective Lithium Leaching of Spent Batteries Cell Powder," Resour. Recycl., 30(6), 45-52 (2021).？
Park, E., Han, C., Son, S. H., Lee, M. S., and Kim, Y. H., "Overview on Pyrometallurgical Recycling Process of Spent Lithium-ion Battery," Resour. Recycl., 31(3), 27-39 (2022).？
Yu, X., Yu, S., Yang, Z., Gao H., Xu P., Cai, G., Rose, S., Brooks, C., Liu, P., and Chen, Z., "Achieving Low-temperature Hydrothermal Relithiation by Redox Mediation for Direct Recycling of Spent Lithium-ion Battery Cathodes," Energy Stor. Mater., 51, 54-62 (2022).？
Moon, H. S., Song, S. J., Tran, T. T., and Lee, M. S., "Separation of Co(II), Ni(II), and Cu(II) from Sulfuric Acid Solution by Solvent Extraction," Resour. Recycl., 31(1), 21-28 (2022).？
Yang, Y., Lei, S., Song, S., Sun, W., and Wang, L., "Stepwise Recycling of Valuable Metals from Ni-rich Cathode Material of Spent Lithium-ion Batteries," Waste Manage., 102, 131-138 (2020).？
Kim, J., Kim, Y., Oh, S. K., and Jeon, J. K., "Analysis of Dry Process Products for Recycling of Spent Secondary Batteries," Clean Technol., 27(2), 139-145 (2021).？
Wu, J., Zheng, M., Liu, T., Wang, Y., Liu, Y., Nai, J., Zhang, L., Zhang, S., and Tao, X., "Direct Recovery: A Sustainable Recycling Technology for Spent Lithium-ion Battery," Energy Stor. Mater., 54, 120-134 (2023).？
Wu, X., Ma J., Wang, J., Zhang, X., Zhou, G., and Liang, Z., "Progress, Key Issues, and Future Prospects for Li-Ion Battery Recycling," Global Chall., 2200067-2200088 (2022)？
Mo, J. Y., "The Benefit-Cost Analysis for Korea Lithium-ion Battery Waste Recycling Project and Promotion Plans," J. Korea Academia-Industrial Cooperation Soc., 19(9), 326-332 (2018).？
Zhou, M., Li, B., Li, J., and Xu, Z., "Pyrometallurgical Technology in the Recycling of a Spent Lithium Ion Battery: Evolution and the Challenge,"ACS EST Engg., 1(10), 1369-1382 (2021).？

상세보기
Chen, J., Li, Q., Song, J., Song, D., Zhang, L., and Shi, X., "Environmentally Friendly Recycling and Effective Repairing of Cathode Powders from Spent LiFePO 4 Batteries," Green Chem., 18(8), 2500-2506 (2016).？

상세보기
Song, X., Hu, T., Liang, C., Long, H. L., Zhou, L., Song, W., Wu, Z. S., and Liu, J. W., "Direct Regeneration of Cathode Materials from Spent Lithium Iron Phosphate Batteries using a Solid Phase Sintering Method," RSC Adv., 7(8), 4783-4790 (2017).？

상세보기
Li, X., Zhang, J., Song, D., Song, D., Song, J., and Zhang, L., "Direct Regeneration of Recycled Cathode Material Mixture from Scrapped LiFePO 4 Batteries," J. Power Sour., 345, 78-84 (2017).？
Song, W., Liu, J., You, L., Wang, S., Zhou, Q., Gao, Y., Yin, R., Xu, W., and Guo, Z., "Re-synthesis of Nano-structured LiFePO 4 /graphene Composite Derived from Spent Lithium-ion Battery for Booming Electric Vehicle Application," J. Power Sour., 419, 192-202 (2019).？
Wang, W. and Wu, Y., "An overview of recycling and treatment of spent LiFePO 4 batteries in China," Resour., Conserv. Recycl., 127, 233-243 (2017).？

상세보기
Yang, Y., Meng, X., Cao, H., Liu, C., Zhang, Y., and Sun, Z., "Selective recovery of lithium from spent lithium iron phosphate batteries: a sustainable process," Green Chem., 20(13), 3121-3133 (2018).？

상세보기
Mahandra, H., and Ghahreman, A., "A sustainable process for selective recovery of lithium as lithium phosphate from spent LiFePO 4 batteries," Resour. Conserv. Recycl., 175, 105883-105894 (2021).？

상세보기
Kumar, J., Shen, X., Li, B., Liu, H., and Zhao, J., "Selective recovery of Li and FePO4 from spent LiFePO 4 cathode scraps by organic acids and the properties of the regenerated LiFePO 4 ," Waste Manag., 113, 32-40 (2020).？
Li, L., Bian, Y., Zhang, X., Yao, Y., Fan, E., Wu, F., and Chen, R., "A green and effective room-temperature recycling process of LiFePO 4 cathode materials for lithium-ion batteries," Waste Manag., 85, 437-444 (2019).？

상세보기
Fan, E., Li, L., Zhang, X., Bian, Y., Xue, Q., Wu, J., Wu, F., and Chen, R., "Selective recovery of Li and Fe from spent lithium-ion batteries by an environmentally friendly mechanochemical approach," ACS Sustain. Chem. Eng., 6(8), 11029-11035 (2018).？
Zhang, J., Hu, J., Liu, Y., Jing, Q., Yang, C., Chen, Y., and Wang, C., "Sustainable and Facile Method for the Selective Recovery of Lithium from Cathode Scrap of Spent LiFePO 4 Batteries," ACS Sustain. Chem. Eng., 7(6), 5626-5631 (2019).？
Liu, K., Liu, L., Tan, Q., and Li, J., "Selective extraction of lithium from a spent lithium iron phosphate battery by mechanochemical solid-phase oxidation," Green Chem., 23(3), 1344-1352 (2021).？

상세보기
Yue, X., Zhang, C., Zhang, W., Wang, Y., and Zhang, F., "Recycling phosphorus from spent LiFePO 4 battery for multifunctional slow-release fertilizer preparation and simultaneous recovery of Lithium," Chem. Eng. J., 426, 131311-131323 (2021).？

상세보기
Peng, D., Zhang, J., Zou, J., Ji G., Ye L., and Zhang, B., "Closed-loop regeneration of LiFePO 4 from spent lithium-ion batteries: A "feed three birds with one scone" strategy toward advanced cathode materials," J. Clean. Prod., 316, 128098-128109 (2021).？

상세보기
Gangaja, B., Nair, S., and Santhanagopalan, D., "Reuse, recycle, and regeneration of LiFePO 4 cathode from spent lithium-ion batteries for rechargeable lithium-and sodium-ion batteries," ACS Sustain. Chem. Eng., 9(13), 4711-4721 (2021).？
Kim, H. S., Kim, D. W., Jang, D. H., Kim, B. R., Jin, Y. H., Chae, B. M., and Lee, S. W., "A Study on the Leaching Effect and Selective Recovery of Lithium Element by Persulfate-based Oxidizing Agents from Waste LiFePO 4 Cathode," Resour. Recycl., 31(4), 40-48 (2022).？
Li, H., Xing, S., Liu, Y., Guo, H., and Kuang, G., "Recovery of Lithium, Iron, and Phosphorus from Spent LiFePO 4 Batteries Using Stoichiometric Sulfuric Acid Leaching System," ACS Sustain. Chem. Eng., 5, 8017-8024 (2017).？
Zheng, R., Zhao, L., Wang, W., Liu, Y., Ma, Q., Mu, D., Li, R., and Dai, C., "Optimized Li and Fe recovery from spent lithium-ion batteries via a solution-precipitation method," RSC Adv., 6, 43613-43625 (2016).？

상세보기
Cai, G., Fung, K., Ng, K., and Wibowo, C., "Process Development for the Recycle of Spent Lithium Ion Batteries by Chemical Precipitation," Ind. Eng. Chem. Res., 53(47), 18245-18259 (2014).？

상세보기
Yang, Y., Zheng, X., Cao, H., Zhao, C., Lin, X., Ning, P., Zhang, Y., Jin, W., and Sun, Z., "A Closed-Loop Process for Selective Metal Recovery from Spent Lithium Iron Phosphate Batteries through Mechanochemical Activation," ACS Sustain. Chem., 5, 9972-9980 (2017).？
Bian, D., Sun, Y., Li, S., Tian, Y., Yang, Z., and Fan, X., "A novel process to recycle spent LiFePO 4 for synthesizing LiFePO 4 /C hierarchical microflowers," Electrochim. Acta, 190, 134-140 (2016).？
Shin, E., Kim, S., Noh, J., Byun, D., Chung, K., Kim, H., and Cho, B., "A green recycling process designed for LiFePO 4 cathode materials for Li-ion batteries," J. Mater. Chem. A, 3(21), 11493-11502 (2015).

상세보기

저자의 다른 논문 :

표제어: PCR

동의어: Packet Collision Rate

용어 설명 출처 목록 (6)

용어 설명: PCR은 세균 특이성이 있는 primer를 이용하여 적은 수의 세균이 있을지라도 쉽게 검출할 수 있는 유용한 방법이며, 이를 이용하여 구강 내 치면세균막이나 타액에서 직접 세균을 검출할 수 있게 되었다[8].

내보내기 구분	파일저장 인쇄 메일전송
구성항목	기본정보 상세정보 관리번호, 논문명, 저널/프로시딩명, 저자 , 발행년, 권, 호, 시작페이지, 끝페이지, 발행기관 관리번호, 논문명, 대등논문명, 저자 , 저널/프로시딩명, 발행기관, 발행년, 발행언어, 권, 호, 시작페이지, 끝페이지, ISBN, ISSN, 주제분야, 키워드, 초록(한글), 초록(영문), 저자(소속기관)
저장형식	Text(ASCII format) Excel format RefWorks Direct Export RIS format (for Reference Manager, ProCite, EndNote), Scholar's Aids, Mendeley
메일정보	받는사람 (필수) @ 보내는사람 (선택) @ 제목 내용 KISTI 검색결과 이메일 서비스
안내	총 건의 자료가 검색되었습니다. 다운받으실 자료의 인덱스를 입력하세요. (1-10,000) 검색결과의 순서대로 최대 10,000건 까지 다운로드가 가능합니다. 데이타가 많을 경우 속도가 느려질 수 있습니다.(최대 2~3분 소요) 다운로드 파일은 UTF-8 형태로 저장됩니다. 파일의 내용이 제대로 보이지 않을실 때는 웹브라우저 상단의 보기 -> 인코딩 -> 자동선택 여부를 확인하십시오. ~ Text(ASCII format) Excel format

연합인증